US2725290A - Development of multi-layer color films with developers containing mercapto azoles - Google Patents

Development of multi-layer color films with developers containing mercapto azoles Download PDF

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Publication number
US2725290A
US2725290A US256369A US25636951A US2725290A US 2725290 A US2725290 A US 2725290A US 256369 A US256369 A US 256369A US 25636951 A US25636951 A US 25636951A US 2725290 A US2725290 A US 2725290A
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United States
Prior art keywords
development
layer
layer color
color films
containing mercapto
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US256369A
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Edward A Smith
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Eastman Kodak Co
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Eastman Kodak Co
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Priority to US256369A priority Critical patent/US2725290A/en
Priority to DEE6286A priority patent/DE1003581B/en
Priority to FR1080483D priority patent/FR1080483A/en
Priority to GB28644/52A priority patent/GB711025A/en
Application granted granted Critical
Publication of US2725290A publication Critical patent/US2725290A/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/407Development processes or agents therefor
    • G03C7/413Developers

Definitions

  • multi-layer photographic elements used for color photography there are usually three differently sensitive emulsion layers coated on one side of a single support. These emulsion layers may contain color couplers for the formation of colored images in the emulsion layers by development with a primary aromatic amino developing agent.
  • One of the difficulties encountered in the development of such multi-layer elements, especially when the development is carried out at high temperatures, is the over-development of the top emulsion layer before the bottom layer is fully developed. This overdevelopment of the top layer is caused by the high rate 'of developer diffusion, developer exhaustion, gelatin swelling within the film, etc. It is obviously a disadvantage since each of the layers of the multi-layer element should be developed at about the same rate or during the same period of time.
  • an object of the present invention to provide a method for preventing the overdevelopment of the top layer of a multi-layer photographic element.
  • a further object is to provide a novel method for developing color images of uniform characteristics in a multi-layer photographic element.
  • a still further object is to provide a method for permitting high temperature development of multi-layer color elements.
  • Mercapto azoles which I have found useful for this purpose are l-phenyl-S-mercapto tetrazole, 4-phenyl-2-mercapto thiazole, Z-mercapto benzoxazole, 2-mercapto benzothiazole, and 1-2-napthyl-5-mercapto tetrazole.
  • Other anti-foggants such as benzotriazole may be present in the developer solution.
  • a multi-layer photographic element of the type described in Mannes and Godowsky U. S. Patent 2,304,940 or Jelley and Vittum U. S. Patent 2,322,027 is used as the multi-layer sensitive material.
  • the sensitive elements of this type comprise a support of cellulose ester, paper or other suitable base having coated thereon a red-sensitive emulsion layer containing a magenta-forming coupler and a blue-sensitive emulsion layer containing a yellow-forming coupler.
  • the couplers may be nited States Patent O minute.
  • the multi-layer element may contain two or more sensitive emulsion layers and may also have filter interlayers, subbing layers, backing layers and overcoating layers applied in the well known manner.
  • One or more of the emulsion layers may also be free of incorporated couplers, the coupler or couplers for these layers being contained in the color developing solution.
  • the exposed multi-layer elements may be processed at temperatures normally used in the processing of photographic films, my invention is especially useful for high temperature processing as, for example, processing at temperatures of about F.
  • the exposed multi-layer element of the type referred to above is processed according to my invention by development directly after exposure in a color developing solution containing the mercapto azole followed by the usual fixing and silver removal steps.
  • the following example illustrates my invention.
  • a multi-layer photographic element having three superposed emulsion layers of the type described in Jelley and Vittum U. S. Patent 2,322,027 was exposed to an image Water to 1 liter.
  • development time will depend on the nature of the particular silver halide emulsions employed by me, for example, development time may be of the order of 1 Development is followed by treatment in an acid hardening fixing bath and a silver removal bath according to well known practices.
  • the amount of anti-foggant used according to my invention may vary from 0.05 gram to 0.5 gram per liter of developer solution. Development may be carried out at temperatures up to about F.
  • the method of preventing overdevelopment of the top emulsion layer of a multi-layer photographic color element having a red-sensitive emulsion layer containing a cyan-forming coupler, a green-sensitive emulsion layer containing a magenta-forming coupler and a blue-sensitive emulsion layer containing a yellow-forming coupler which comprises exposing said element and developing it directly to colored images at about 130 F. with a solution of a primary aromatic amino developing agent containing 0.1 gram per liter of developing solution of 1- phenyl-S-mercapto tetrazole.

Description

Edward A. Smith, Rochester, N. Y., assignor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey No Drawing. Application November 14, 1951, Serial No. 256,369
1 Claim. (Cl. 95-2) This application relates to photography and particularly to the processing of multi-layer color films or papers.
In multi-layer photographic elements used for color photography there are usually three differently sensitive emulsion layers coated on one side of a single support. These emulsion layers may contain color couplers for the formation of colored images in the emulsion layers by development with a primary aromatic amino developing agent. One of the difficulties encountered in the development of such multi-layer elements, especially when the development is carried out at high temperatures, is the over-development of the top emulsion layer before the bottom layer is fully developed. This overdevelopment of the top layer is caused by the high rate 'of developer diffusion, developer exhaustion, gelatin swelling within the film, etc. It is obviously a disadvantage since each of the layers of the multi-layer element should be developed at about the same rate or during the same period of time.
It is, therefore, an object of the present invention to provide a method for preventing the overdevelopment of the top layer of a multi-layer photographic element. A further object is to provide a novel method for developing color images of uniform characteristics in a multi-layer photographic element. A still further object is to provide a method for permitting high temperature development of multi-layer color elements. Other objects will be apparent from the following description of my invention.
These objects are accomplished by color developing the exposed photographic element with a solution of a primary aromatic amino developing agent containing an azole having a mercapto substituent. This agent acts as an anti-foggant and diffuses more slowly than the other de- .veloper constituents, or varies in etfectiveness with depth of penetration because of the insolubility of the silver salt of the anti-foggant, and thereby reduces or prevents overdevelopment of the top layer before the bottom layer is fully developed.
Mercapto azoles which I have found useful for this purpose are l-phenyl-S-mercapto tetrazole, 4-phenyl-2-mercapto thiazole, Z-mercapto benzoxazole, 2-mercapto benzothiazole, and 1-2-napthyl-5-mercapto tetrazole. Other anti-foggants such as benzotriazole may be present in the developer solution.
According to my invention a multi-layer photographic element of the type described in Mannes and Godowsky U. S. Patent 2,304,940 or Jelley and Vittum U. S. Patent 2,322,027 is used as the multi-layer sensitive material. The sensitive elements of this type comprise a support of cellulose ester, paper or other suitable base having coated thereon a red-sensitive emulsion layer containing a magenta-forming coupler and a blue-sensitive emulsion layer containing a yellow-forming coupler. The couplers may be nited States Patent O minute.
"ice
2 of the composition and incorporated in the manner described in Mannes and Godowsky U. S. Patent 2,304,940 .or Jelley and Vittum U. S. Patent 2,322,027.
Obviously the multi-layer element may contain two or more sensitive emulsion layers and may also have filter interlayers, subbing layers, backing layers and overcoating layers applied in the well known manner. One or more of the emulsion layers may also be free of incorporated couplers, the coupler or couplers for these layers being contained in the color developing solution.
While the exposed multi-layer elements may be processed at temperatures normally used in the processing of photographic films, my invention is especially useful for high temperature processing as, for example, processing at temperatures of about F.
The exposed multi-layer element of the type referred to above is processed according to my invention by development directly after exposure in a color developing solution containing the mercapto azole followed by the usual fixing and silver removal steps. The following example illustrates my invention.
' A multi-layer photographic element having three superposed emulsion layers of the type described in Jelley and Vittum U. S. Patent 2,322,027 was exposed to an image Water to 1 liter.
The time of development will depend on the nature of the particular silver halide emulsions employed by me, for example, development time may be of the order of 1 Development is followed by treatment in an acid hardening fixing bath and a silver removal bath according to well known practices.
The amount of anti-foggant used according to my invention may vary from 0.05 gram to 0.5 gram per liter of developer solution. Development may be carried out at temperatures up to about F.
It will be understood that the modifications and examples included herein are illustrative only and that my invention is to be taken as limited only by the scope of the appended claim.
What I claim is:
The method of preventing overdevelopment of the top emulsion layer of a multi-layer photographic color element having a red-sensitive emulsion layer containing a cyan-forming coupler, a green-sensitive emulsion layer containing a magenta-forming coupler and a blue-sensitive emulsion layer containing a yellow-forming coupler, which comprises exposing said element and developing it directly to colored images at about 130 F. with a solution of a primary aromatic amino developing agent containing 0.1 gram per liter of developing solution of 1- phenyl-S-mercapto tetrazole.
References Cited in the file of this patent UNITED STATES PATENTS 2,159,600 Murray et al. May 23, 1939 2,476,541 Friedman July 19, 1949 2,553,498 Duerr May 15, 1951
US256369A 1951-11-14 1951-11-14 Development of multi-layer color films with developers containing mercapto azoles Expired - Lifetime US2725290A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US256369A US2725290A (en) 1951-11-14 1951-11-14 Development of multi-layer color films with developers containing mercapto azoles
DEE6286A DE1003581B (en) 1951-11-14 1952-11-08 Process for preventing overdevelopment of the top emulsion layer of halogen silver multilayer materials during color development
FR1080483D FR1080483A (en) 1951-11-14 1952-11-13 Process for processing color photographic emulsions and their applications
GB28644/52A GB711025A (en) 1951-11-14 1952-11-13 Improvements in the processing of exposed multilayer photographic materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US256369A US2725290A (en) 1951-11-14 1951-11-14 Development of multi-layer color films with developers containing mercapto azoles

Publications (1)

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US2725290A true US2725290A (en) 1955-11-29

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US (1) US2725290A (en)
DE (1) DE1003581B (en)
FR (1) FR1080483A (en)
GB (1) GB711025A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1174160B (en) * 1960-08-22 1964-07-16 Polaroid Corp Process for the production of multicolor transfer images
US3260604A (en) * 1963-11-19 1966-07-12 Eastman Kodak Co Photographic colloid transfer system
US3260597A (en) * 1960-12-02 1966-07-12 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers and development arrestors
US3265498A (en) * 1960-08-22 1966-08-09 Polaroid Corp Diffusion transfer photographic process utilizing development restrainers
DE1282455B (en) * 1960-11-23 1968-11-07 Eastman Kodak Co Dye developer diffusion process and image receiving layer for carrying out the process
US4355092A (en) * 1981-01-05 1982-10-19 Polaroid Corporation Novel phenylmercaptoazole compounds
US4355101A (en) * 1981-01-05 1982-10-19 Polaroid Corporation Phenylmercaptoazole compounds
US4390613A (en) * 1981-01-05 1983-06-28 Polaroid Corporation Diffusion transfer photographic system utilizing substituted phenylmercaptoazoles
US4593108A (en) * 1981-01-05 1986-06-03 Polaroid Corporation 1-phenyl-5-mercapto tetrazoles

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4963475A (en) * 1986-04-22 1990-10-16 Konishiroku Photo Industry Co., Ltd. Method for processing silver halide photo-sensitive material
JP2591616B2 (en) * 1986-04-22 1997-03-19 コニカ株式会社 Processing method of silver halide photographic light-sensitive material in which fog is prevented

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2159600A (en) * 1936-02-06 1939-05-23 Veracol Film Syndicate Ltd Production of composite photographic images
US2476541A (en) * 1947-11-18 1949-07-19 Gen Aniline & Film Corp Process for producing multilayer color negatives containing masking images for colorcorrection purposes
US2553498A (en) * 1947-11-18 1951-05-15 Gen Aniline & Film Corp First developer for multilayer color film of the reversal type

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2271229A (en) * 1939-11-10 1942-01-27 Eastman Kodak Co Fog inhibitor for photographic developers
GB583648A (en) * 1944-11-13 1946-12-23 John David Kendall Improvements in photographic materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2159600A (en) * 1936-02-06 1939-05-23 Veracol Film Syndicate Ltd Production of composite photographic images
US2476541A (en) * 1947-11-18 1949-07-19 Gen Aniline & Film Corp Process for producing multilayer color negatives containing masking images for colorcorrection purposes
US2553498A (en) * 1947-11-18 1951-05-15 Gen Aniline & Film Corp First developer for multilayer color film of the reversal type

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1174160B (en) * 1960-08-22 1964-07-16 Polaroid Corp Process for the production of multicolor transfer images
US3265498A (en) * 1960-08-22 1966-08-09 Polaroid Corp Diffusion transfer photographic process utilizing development restrainers
DE1288911B (en) * 1960-08-22 1969-02-06 Polaroid Corp Dye diffusion process
DE1282455B (en) * 1960-11-23 1968-11-07 Eastman Kodak Co Dye developer diffusion process and image receiving layer for carrying out the process
US3260597A (en) * 1960-12-02 1966-07-12 Eastman Kodak Co Photographic multicolor diffusion transfer process using dye developers and development arrestors
US3260604A (en) * 1963-11-19 1966-07-12 Eastman Kodak Co Photographic colloid transfer system
US4355092A (en) * 1981-01-05 1982-10-19 Polaroid Corporation Novel phenylmercaptoazole compounds
US4355101A (en) * 1981-01-05 1982-10-19 Polaroid Corporation Phenylmercaptoazole compounds
US4390613A (en) * 1981-01-05 1983-06-28 Polaroid Corporation Diffusion transfer photographic system utilizing substituted phenylmercaptoazoles
US4593108A (en) * 1981-01-05 1986-06-03 Polaroid Corporation 1-phenyl-5-mercapto tetrazoles

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GB711025A (en) 1954-06-23
FR1080483A (en) 1954-12-09
DE1003581B (en) 1957-02-28

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